Silver halide photographic light-sensitive material

ABSTRACT

Disclosed is a silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer, a hydrazine compound is contained in said silver emulsion layer or at least one of other layers, wherein said material contains at least one compound represented by Formula I or Formula II, ##STR1## wherein R 1  and R 2  each independently represent an alkyl group, an alkenyl group or an alkynyl group respectively; R 1  and R 2  may form a ring; R 3  represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; L 1  represents a divalent linking group; X represents a --[S--L 2  --Y--(L 3 )n]-- group or a [--(L 3 )n--Y--L 2  --S--]-- group, L 2  represents an alkylene group or an alkenylene group, Y represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, L 3  represents ##STR2## wherein Z 1 , Z 2  and Z 3  each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; n is an integer of 0 to 1; ##STR3## wherein R4, R5 and R 6  each independently represent an alkyl group, an alkenyl group or an alkynyl group, further Formula II comprises a thioether structure and a --O--Y) l  structure, Y represents an alkylene group, an alkenylene group or an arylene group, l is an integer of 2 or more. 
     The silver halide photographic light-sensitive material is capable offering high contrast.

FIELD OF THE INVENTION

The present invention relates to a photographic light-sensitive materialcomprising a support having thereon silver halide light-sensitivelayers, and more particularly to a silver halide photographiclight-sensitive material capable of offering high contrast.

BACKGROUND OF THE INVENTION

In a photographic plate-making process, a step to convert a documentwith continuous gradation to dot images is included. For this step, atechnology employing infectious development has been used as aphotographic technology capable of offering super high contrast imagereproduction.

Litho-type silver halide photographic light-sensitive materials used forinfectious development are, for example, composed of silverbromochloride emulsion having an average grain size of 0.2 μm and highsilver chloride content ratio (at least 50 mol % or more) wherein grainsize distribution is narrow and the shape of grain is uniform. Byprocessing the above-mentioned litho-type silver halide photographiclight-sensitive material with an alkaline hydroquinone developingsolution with low sulfite ion density, images having high contrast, highsharpness and high resolution can be obtained.

However, since the above-mentioned litho-type developing solutions aresubjected to air oxidation, it is extremely inferior in preservability.Therefore, it is also difficult to keep the quality of developmentconstant in continuous use.

Methods for obtaining images having high contrast rapidly withoutemploying the above-mentioned litho-type developing solutions are known.As shown in U.S. Pat. No. 2,419,975 and Japanese Patent Publication Opento Public Inspection (hereinafter, referred to as Japanese Patent O.P.I.Publication) Nos. 16623/1976, 20921/1976 and 106244/1981, it representsa method to contain hydrazine derivatives in silver halidelight-sensitive materials.

Due to the above-mentioned method, sulfite ion density in a developingsolution can be kept high and processing can be conducted while keepinghigh preservability.

However, in the above-mentioned method, processing had to be conductedwith developing solution having pH of 11 or more in order to utilize thehigh contrast property of hydrazine derivatives to a full extent. Thoughdeveloping solutions having pH of 11 or more is more stable than alitho-type developing wherein the developing agent is easily oxidizedwhen it is exposed to air, it often fails to offer super high contrastimages due to the oxidation of developing agent.

In order to complement the above-mentioned defect, silver halidephotographic light-sensitive materials containing nucleating agentswhich make images contrast-increasing even in a developing solution withrelatively low pH are disclosed in Japanese Patent O.P.I. PublicationNo. 29751/1988 and European Patent Nos. 333,435 and 345,025.

However, when silver halide photographic light-sensitive materialscontaining the above-mentioned nucleating agents are processed withdeveloping agent having pH of less than 11, it is the present situationthat contrast-increase is incomplete and satisfactory dot propertiescannot be obtained.

On the other hand, in European Patent No. 364,166 and Japanese PatentO.P.I. Publication Nos. 222241/1987, 140340/1985, 250439/1987 and280733/1987, contrast-promoting compounds for acceleratingcontrast-increase are described. It is sure that dot properties areimproved by adding the above-mentioned compounds into emulsion layers.However, it turned out that a problem of sand-like and pinhole-likefogging in dots, so-called pepper fog, occurred damaging the quality ofdot images.

Therefore, there has been demanded a light-sensitive material solvingthe above-mentioned problems and employing effective nucleating agentsand contrast-promoting compounds.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a silver halidephotographic light-sensitive material showing preferable dot propertiesby inhibiting fog occurrence in dot images as well as high-contrastphotographic properties even processed with a developing solution withpH of less than 11.

The above-mentioned object of the present invention was attained by asilver halide photographic light-sensitive material having the followingstructure. A silver halide photographic light-sensitive materialcomprising a support having thereon at least one silver halide emulsionlayer, said silver halide emulsion or at least one of other structurallayers containing a hydrazine compound, wherein at least one ofcompounds represented by the following Formula I or II is contained.##STR4## wherein R₁ and R₂ each independently represent an alkyl group,an alkenyl group or an alkynyl group respectively; R₁ and R₂ may form aring; R₃ represents a hydrogen atom, an alkyl group, an alkenyl group,an alkynyl group, an aryl group or a heterocyclic group; L₁ represents adivalent linking group; X represents

    --S--L.sub.2 --Y--(L.sub.3).sub.n ] group or --(L.sub.3).sub.n Y--L.sub.2 --S-- group;

L₂ represents an alkylene group or an alkenylene group; Y represents acarbonyl group, a sulfonyl group, a sulfoxy group and a phosphorylgroup; L₃ represents ##STR5##

Z₁, Z₂ and Z₃ each independently represent a hydrogen atom, an alkylgroup, an alkenyl group, an alkynyl group, an aryl group or aheterocycle; n represents 0 or 1. ##STR6## wherein R₄, R₅ and R₆ eachindependently represent an alkyl group, an alkenyl group and an alkynylgroup. However, compounds having Formula II have a partial structure ofthioether and

    --O--Y).sub.l

Y represents a substitutable alkylene group, a substitutable alkenylenegroup or a substitutable arylene group; l represents an integer of 2 ormore.

(2) The silver halide photographic light-sensitive material described in(1) wherein hydrazine compounds described in (1) are represented by thefollowing Formula IV. ##STR7## wherein R₇ represents an aryl group or aheterocycle; R₈ represents ##STR8##

R₉ and R₁₀ represent a hydrogen atom, an alkyl group, an alkenyl group,an alkynyl group, an aryl group, a heterocycle, an amino group, ahydroxyl group, an alkoxy group, an alkenyloxy group, an alkinyloxygroup, an aryloxy group or a heterocyclic oxy group; R₁₁ represents ahydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, anaryl group or a heterocycle; both A₁ and A₂ both represent hydrogenatoms, or one of them is a hydrogen atom while the other of them is anacyl group, a sulfonyl group or an oxalyl group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereunder, we will explain the present invention in detail.

In Formula I, as groups represented by R₁ and R₂, alkyl groups (forexample, a methyl group, an ethyl group, a propyl group, an isopropylgroup, a butyl group, an octyl group and a dodecyl group), alkenylgroups (for example, an allyl group and a butenyl group), alkynyl groups(for example, a propargyl group and a butynyl group) are cited. Theabove-mentioned groups may further be substituted with substituents (forexample, an aryl group, an alkoxy group, an aryloxy group, a hydroxylgroup, an alkylthio group, an arylthio group, a sulfonamide group, acarbonamide group, an ureido group, a sulfamoyl group, a carbamoylgroup, an amino group, an alkoxycarbonyl group and a carboxyl group). R₁and R₂ may be combined to form a ring (for example, a piperidine, apiperazine, a morpholine and a pyrrolidine). As R₁ and R₂, alkyl groupsare preferable and those having 2 to 20 carbons are most preferable.

As groups represented by R₃, alkyl groups (for example, a methyl group,an ethyl group, a propyl group, a t-butyl group, an octyl group and adodecyl group), alkenyl groups (for example, an allyl group and abutenyl group), alkynyl groups (for example, a propargyl group and abutynyl group), aryl groups (for example, a phenyl group and a naphtylgroup) or a heterocycles (for example, a thienyl group, a furyl groupand a pyridyl group).

The above-mentioned groups may further be substituted with the samesubstituents as explained in R₁ and R₂.

L₁ represents a divalent linking group, and preferably a group having asubstitutable alkylene group (provided that said alkylene combines with##STR9##

Of divalent linking groups represented by L₁, the preferable arealkylene groups having 1 to 10 carbons and groups formed in combinationof an alkylene group having 1 to 10 carbons and a group illustrated asfollows; ##STR10##

X represents

    --S--L.sub.2 --Y--L.sub.3).sub.n ] group [(L.sub.3).sub.n Y--L.sub.2 --S-- group

L₂ represents an alkylene group (for example, a methylene group, anethylene group, a propylene group and a butylene group) or an alkenylenegroup (for example, a propenylene group and a butenylene group);preferable L₂ is an alkylene group having 1 to 4 carbons and morepreferable L₂ is a methylene group and an ethylene group; Y represents acarbonyl group, a sulfonyl group, a sulfoxy group or a phosphoryl groupand preferably a carbonyl group or a sulfonyl group; L₃ represents##STR11##

Z₁, Z₂ and Z₃ each independently represent a hydrogen atom, an alkylgroup, an alkenyl group, an alkynyl group, an aryl group or aheterocycle. Z₁, Z₂ and Z₃ are each independently preferable to be ahydrogen atom, an alkyl group or an aryl group.

n represents 0 or 1.

Hereunder, we will show practical examples of the compounds representedby Formula I. However, it should be understood that the presentinvention is by no means restricted to such specific examples. ##STR12##

Next, we will show how to obtain and how to synthesize compoundsillustrated by the following Formula I.

How to obtain compound I-2

Compound I-2 is available from BADER Co., Ltd. through the market (thecatalogue number is S42233-9).

How to obtain compound I-4

Compound I-4 is available from BADER Co., Ltd. through the market (thecatalogue number is S42128-6).

Synthesis of compound I-3

Compound I-3 can be synthesized in accordance with the followingsynthetic method. ##STR13##

After 7 g of 1-naphthylamine and 280 ml of acetic acid were mixed, 4.64g of pyridine was added thereto. While the solution was chilled by meansof ice water bath, 7.21 g of chloroacetyl chloride was dropped thereon.Then, the solution was agitated for 30 minutes at room temperature.After adding 200 ml of water, the solution was agitated for 5 minutes.Then, coagulated crystals were filtrated out. After this crude crystalswere dispersed with 100 ml of isopropylether for 10 minutes, they werefiltrated out. Thus, compound (A) was obtained.

The amount obtained was 6.14 g (the yield was 57%) White crystal

After 3.87 g of diethylaminoethanetiol-hydrochloride and 100 ml ofethanol were mixed, 1.82 g of sodium hydroxide was added thereto whilethe solution was agitated at room temperature. Then, the solution wasagitated for 20 minutes. To the solution, 5 g of compound (A)synthesized in the above-mentioned manner was added. Then, the solutionwas agitated for 2 hours at the internal temperature of 50° C. To thesolution, 100 ml of sodium hydroxide aqueous solution having pH of 13was added. Then, the solution was extracted 3 times with 50 ml ofisopropylether. The obtained organic layer was extracted 4 times with200 ml of hydrochloric acid aqueous solution having pH of 1, and thewater layer was extracted 4 times with 200 ml of isopropylether afterits pH was adjusted to 13 with sodium hydroxide. After the organic layerwas washed twice with 500 ml of water, the solvent was removed. Theobtained oil product was refined by means of silica gel columnchromatography (Wakogel C-200, chloroform-methanol (10/1)). Thus,compound I-3 was obtained.

The amount obtained was 5.59 g (the yield was 77%) White amorphous solid

Synthesis of compound I-11

Compound I-11 can be synthesized in accordance with the followingsynthesis scheme. ##STR14##

Synthesis of compound I-12

Compound I-12 can be synthesized in accordance with the followingsynthesis scheme. ##STR15##

Synthesis of compound I-17

Compound I-17 can be synthesized in accordance with the followingsynthesis scheme. ##STR16##

Synthesis of compound I-20

Compound I-20 can be synthesized in accordance with the followingsynthesis scheme. ##STR17##

Synthesis of compound I-22

Compound I-22 can be synthesized in accordance with the followingsynthesis scheme. ##STR18##

Synthesis of compound I-34

Compound I-34 can be synthesized in accordance with the followingsynthesis scheme. ##STR19##

Synthesis of compound I-44

Compound I-44 can be synthesized in accordance with the followingsynthesis scheme. ##STR20##

In Formula II, R₄ and R₅ each independently represent an alkyl group(for example, a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an octyl group and a dodecyl group), analkenyl group (for example, an allyl group, a 2-methylallyl group and abutenyl group), or an alkynyl group (for example, a propargyl group anda butynyl group). They may be substituted with substituents (forexample, an alkyl group, an aryl group, an alkoxy group, an aryloxygroup, a hydroxyl group, an alkylthio group, an arylthio group, asulfonamide group, a carbonamide group, an ureido group, a sulfamoylgroup, a carbamoyl group, an amino group, an alkoxycarbonyl group and acarboxyl group). R₄ and R₅ may be combined to form a ring (for example,a piperidine, a piperadine, a morpholine and a pyrrolidine). As R₄ andR₅, an alkyl group and an alkenyl group are preferable and an alkylgroup having 2 to 20 carbons and an alkenyl group having 3 to 20 carbonsare most preferable.

R₆ represents, an alkyl group (for example, a methyl group, an ethylgroup, a propyl group, a butyl group, an octyl group and a dodecylgroup), an alkenyl group (for example, an allyl group and a butenylgroup), an alkynyl group (for example, a propargyl group and a butynylgroup), an aryl group (for example, a phenyl group and a naphtyl group)or a heterocyclic group (for example, a thienyl group, a furyl group anda pyridyl group).

They may be substituted with the same substituents as explained in R₄and R₅.

Of the above-mentioned Formula II, the preferable are compoundsillustrated by the following Formulas II-A and II-B. ##STR21## whereinR₄, R₅, Y and l represent the same groups as those in Formula II; Lrepresents a divalent aliphatic group; J₁ and J₂ represent a divalentlinking groups; m and n represent 0 or 1; R' represents an aliphaticgroup, an aromatic group or a heterocycle, R" represents a hydrogenatom, an aliphatic group, an aromatic group or a heterocyclic group.

As divalent aliphatic groups represented by L, an alkylene group(preferably having 1 to 20 carbons) and an alkenylene group (preferablyhaving 3 to 20 carbons); as L, an alkylene groups is preferable and analkylene group having 2 to 10 carbons is more preferable;

As L, an ethylene group, a trimethylene group and a tetramethylene groupare most preferable;

L may be substituted by appropriate substituents (for example, an alkylgroup and an aryl group);

As divalent linking groups represented by J₁ and J₂, the followinggroups, groups composed of the combination of the following groups andsubstituents appropriate therefor (for example, an alkyl group, analkenyl group, an alkynyl group, an aryl group, a heterocycle, aheterocyclic onium group, an amino group, an ammonium group, anacylamino group, a carbamoyl group, a sulfonamide group, a sulfamoylgroup, an ureido group, an alkoxy group, an aryloxy group, aheterocyclic oxy group, a hydroxyl group, an alkoxycarbonylamino group,an alkylthio group, an arylthio group, a heterocyclic thio group, asulfonyl group, a sulfinyl group, a halogen atom, a cyano group, a sulfogroup, a carboxyl group, an acyloxy group, an acyl group, analkyloxycarbonyl group, an aryloxycarbonyl group, a nitro group, athioacyl group, a thioacylamino group and a thioureido group) are; --CH₂--, --CH═CH--, --C₆ H₄ --, pyridinediyl, --N(Z₁)-- (Z₁ represents ahydrogen atom, an alkyl group or an aryl group), --O--, --S--, --CO--,--SO₂, --CH═N--;

m and n represent 0 or 1 independently, though both of them arepreferable to be 0;

Y represents an alkylene group (for example, an ethylene group, apropylene group, a trimethylene group and a tetramethylene group), analkenylene group (for example, a vinylene group, a propenylene group, a1-butenylene and a 2-butenylene group) and groups having appropriatesubstituents therefor (for example, as appropriate substituentscontained in J₁ and J₂, those mentioned above);

Y is preferable an alkylene group, and more preferable an ethylenegroup, a propylene group and a trimethylene group;

As aliphatic groups independently represented by R' and R", astraight-chained, branch-chained or ring alkyl group, alkenyl group oralkynyl group (preferably, an alkyl group having 1 to 20 carbons atalkyl group, an alkenyl group having 2 to 20 carbons at alkenyl groupand an alkynyl group having 2 to 20 carbons) are cited;

As aromatic groups independently represented by R' and R", aryl groupsof mono-ring (for example, benzene) or condensed ring (for example,naphthalene) are preferable;

As heterocyclic groups independently represented by R' and R",heterocyclic groups of mono-ring or condensed ring containing at least ahetero atom selected from nitrogen, sulfur and oxygen are preferable,and 5-membered groups (for example, pyrrole, thiophene, furan,imidazole, pyrazole, thiazole, oxazole, thiadiazole, oxadiazole,pyrroline, pyrrolidine, imidazoline, pyrazolidine and tetrahydrofuran),6-membered groups (for example, pyridine, pyrazine, pyrimidine,pyridazine, triazine, dithin, dioxane, piperidine, morpholine andquinuclidine) and groups of condensed ring between the above-mentionedgroups and a cycloalkyl ring (for example, cyclopentane, cyclohexane andcycloheptane), a cycloalkenyl ring (for example, cyclopentene,cyclohexane and cycloheptene), an aromatic ring (for, example, benzeneand naphthalene) and a heterocycle (for example, pyrrole, imidazole,pyridine, pyrazine and pyrimidine).

Next, we will show practical examples of compounds illustrated byFormula II in the present invention. ##STR22##

Next, we will show synthesized agents of the compounds illustrated byFormula II.

For example, compound II-3 is synthesized by means of the followingsynthesizing method. ##STR23##

For example, compound II-4 can be synthesized employing a synthesizedintermediate (a) of the above-mentioned II-3. ##STR24##

The content of compounds represented by Formula I or Formula II in thepresent invention are preferably 5×10⁻⁷ to 5×10⁻¹ mol per mol of silverhalide. Especially, it is preferable within the range of 5×10⁻⁶ to5×10⁻².

In the present invention, when compounds represented by Formula I orFormula II are contained in a photographic light-sensitive material,they are contained in silver halide emulsion layers or hydrophiliccolloidal layers adjacent to said silver halide emulsion layers.

Here, compounds represented by Formula I or Formula II may be containedin the same layers as for hydrazine compounds, or they may be containedin different layers.

As hydrazine compounds used in the present invention, those representedby Formula III are preferable. ##STR25## wherein A represents analiphatic group, an aromatic group or a heterocyclic group; B representsan acyl group, an alkylsulfonyl group, an arylsulfonyl group, analkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, asulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, athiocarbamoyl group, an oxalyl group or a heterocyclic group; both A₁and A₂ represent hydrogen atoms, or one of them is a hydrogen atom whilethe other of them is an acyl group, a sulfonyl group or an oxalyl group,wherein B, A₂ and a nitrogen atom bonded with B and A₂ may form apartial structure of a hydrazone shown below. ##STR26##

Hereunder, we will explain Formula III further in detail.

An aliphatic group represented by A is preferably those having 1 to 30carbons, especially straight-chained, branched-chained or ring alkylgroups having 1 to 20 carbons. For example, a methyl group, an ethylgroup, a t-butyl group, an octyl group, a cyclohexyl group and a benzylgroup are cited, which may be substituted with appropriate substituents(for example, an aryl group, an alkoxyl group, an aryloxy group, analkylthio group, an arylthio group, a sulfoxy group, a sulfonamidegroup, an acylamino group and an ureido group).

The preferable aromatic groups represented by A in Formula III are arylgroups of mono-ring or condensed-ring. For example, a benzene ring or anaphthalene ring may be cited.

As a heterocyclic group represented by A in Formula III, the preferableare heterocycles of mono-ring or condensed ring containing a hetero atomselected from at least one of nitrogen, sulfur and oxygen. For example,pyrrolidine, imidazole, tetrahydrofuran, morpholine, pyridine,pyrimidine, quinoline, thiazole, benzothiazole, thiophene and furan maybe cited.

As A, the especially preferable, are an aryl group and a heterocyclicgroup.

A, an aryl group and a heterocyclic group, may have a substituent. Astypical substituents, an alkyl group (preferably having 1 to 20carbons), an aralkyl group (preferably those of mono-ring or condensedring having 1 to 3 carbons at alkyl portion), an alkoxyl group(preferably having 1 to 20 carbons at alkyl portion), substituted aminogroup (preferably amino group substituted with an alkyl group or analkylidene groups having 1 to 20 carbons), an acylamino group(preferably having 1 to 40 carbons), a sulfonamide groups (preferablyhaving 1 to 40 carbons), an ureido group (preferably having 1 to 40carbons), a hydrazinocarbonylamino group (preferably those having 1 to40 carbons), a hydroxyl group and a phosphoamide group (preferablyhaving 1 to 40 carbons) is cited.

B represents an acyl group (for example, a formyl group, an acetylgroup, a propionyl group, a trifluoroacetyl group, a methoxyacetylgroup, a phenoxyacetyl group, a methylthioacetyl group, a chloroacetylgroup, a benzoyl group, a 2-hydroxymethylbenzoyl group and a4-chlorobenzoyl group), an alkylsulfonyl group (for example, amethanesulfonyl group and a 2-chloroethanesulfonyl group), anarylsulfonyl group (for example, a benzenesulfonyl group), analkylsulfinyl group (for example, a methanesulfinyl group), anarylsulfinyl group (for example, a benzenesulfinyl group), an carbamoylgroup (for example, a methylcarbamoyl group and a phenylcarbamoylgroup), an alkoxycarbonyl group (for example, a methylcarbonyl group anda methoxyethoxycarbonyl group), an aryloxycarbonyl group (for example, aphenoxycarbonyl group), a sulfamoyl group (for example, adimethylsulfamoyl group), a sulfinamoyl group (for example, amethylsulfinamoyl group), an alkoxysulfonyl group (for example, amethoxysulfonyl group), a thioacyl group (for example, amethylthiocarbonyl group), a thiocarbamoyl group (for example, amethylthio carbamoyl group), a thiocarbamoyl group (for example, amethylthiocarbamoyl group), an oxalyl group (mentioned later in relationto Formula II) or a heterocyclic group is cited.

B in Formula III may form ##STR27## together with A₂ and a nitrogen atomwith which B and A₂ couple together.

R₁₂ represents an alkyl group, an aryl group or a heterocyclic group.R₁₃ represents a hydrogen atom, an alkyl group, an aryl group or aheterocyclic group.

As B, an acyl group or an oxalyl group are especially preferable.

Both A₁ and A₂ are hydrogen atoms, or one of them is a hydrogen atomwhile the other is an acyl group (for example, an acetyl group, atrifluoroacetyl group and a benzoyl group), a sulfonyl group (amethanesulfonyl group and a toluenesulfonyl group) or an oxalyl group(an ethoxalyl group).

The particularly preferable of the hydrazine compounds used in thepresent invention are those illustrated by the following Formula IV.##STR28## wherein R₇ represents an aryl group or a heterocyclic group;R₈ represents ##STR29##

R₉ and R₁₀ each independently represent a hydrogen atom, an alkyl group,an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group,an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group,an alkynyloxy group, an aryloxy group or a heterocyclicoxy group. R₁₁represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynylgroup, an aryl group or a heterocyclic group. A₁ and A₂ represent thesame group as A₁ and A₂ in Formula III.

We will explain Formula IV further in detail.

As aryl groups represented by R₇, those of mono-ring or condensed ringare preferable. For example, benzene or naphthalene may cited.

As a heterocycle represented by R₇, 5-membered or 6-membered unsaturatedheterocycles of mono-ring or condensed ring containing at least onehetero atom selected from nitrogen, sulfur and oxygen are preferable.For example, pyridine, quinoline, pyrimidine, thiophene, furan, thiazoleor benzothiazole are cited.

As R₇, the preferable is an aryl group, and those having a benzene ringare most preferable.

A₁ and A₂ represent the same group as A₁ and A₂ in Formula III. Both arepreferable to be hydrogen atoms.

R₈ represents ##STR30## Here, R₉ and R₁₀ each independently represent ahydrogen atom, an alkyl group (for example, a methyl group, an ethylgroup and a benzyl group), an alkenyl group (for example, an allyl groupand a butenyl group), an alkynyl group (for example, a propargyl groupand a butynyl group), an aryl group (for example, a phenyl group and anaphtyl group), a heterocyclic group (for example,2,2,6,6-tetramethylpiperidinyl group, a N-benzylpiperidinyl group, aquinuclidinyl group, a N,N'-diethylpyrazolyzynyl group, aN-benzylpyrrolidinyl group and a pyridyl group), an amino group (forexample, an amino group, a methylamino group, a dimethylamino group anda dibenzylamino group), a hydroxyl group, an alkoxyl group (for example,a methoxy group and an ethoxy group), an alkenyloxy group (for example,an allyloxy group), an alkynyloxy group (for example, a propargyloxygroup), an aryloxy group (for example, a phenoxy group) or aheterocyclicoxy group (for example, a pyridyloxy group). R₉ and R₁₀ mayform a ring (for example, piperidine and morpholine) together with anitrogen atom. R₁₁ represents a hydrogen atom, an alkyl group (forexample, a methyl group, an ethyl group, a methoxyethyl group and ahydroxyethyl group), an alkenyl group, (for example, an allyl group anda butenyl group), an alkynyl group (for example, a propargyl group and abutenyl group), an aryl group (for example, a phenyl group and a naphtylgroup) and a heterocyclic group (for example, a2,2,6,6-tetramethylpiperidinyl group, a N-methylpiperidinyl group and apyridyl group).

Hereunder, we will show practical examples of Formula III. ##STR31##

Compounds represented by Formula III in the present invention can besynthesized with reference to methods described in Japanese PatentO.P.I. Publication Nos. 180361/1987, 178246/1987, 234245/1988,234246/1988, 90439/1989, 37/1990, 841/1990, 947/1990, 120736/1990,230233/1990 and 125134/1991, U.S. Pat. Nos. 4,686,167, 4,988,604 and4,994,365 and European Patent Nos. 253,665 and 333,435.

Content of compounds represented by Formula III in the present inventionis preferably 5×10⁻⁷ to 5×10⁻¹ mol per mol of silver halide and morepreferably 5×10⁻⁶ to 5×10⁻² mol.

In the present invention, when compounds represented by Formula III arecontained in a photographic light-sensitive material, they are containedin a silver halide emulsion layer or a hydrophilic colloidal layeradjacent to said silver halide emulsion layer.

A silver halide photographic light-sensitive material in the presentinvention has at least one silver halide emulsion layer. At least onesilver halide emulsion layer may be provided on one side of support, orat least one layer may be provided on each of both sides of the support.This silver halide emulsion can be coated on a support directly or itcan be coated on a support through another layer, for example, ahydrophilic colloidal layer not containing a silver halide emulsion. Inaddition, on a silver halide emulsion layer, a hydrophilic colloidallayer as a protective layer may be coated. In addition, a silver halideemulsion layer may be coated in the form of different kinds of silverhalide emulsion layers, for example, a high sensitive silver halideemulsion layer and a low sensitive silver halide emulsion layer. In sucha case, an intermediate layer may be provided between silver halideemulsion layers. Namely, an intermediate layer composed of hydrophiliccolloid can be provided, if necessary. In addition, between a silverhalide emulsion layer and a protective layer, nonsensitive hydrophiliccolloidal layers such as an intermediate layer, a protective layer, ananti-halation layer and a backing layer may be provided.

Next, we will explain silver halide used for a silver halidephotographic light-sensitive material in the present invention. Assilver halide, silver chloroiodidobromide containing silver iodide of 4mol % or less, preferably silver iodide of 3 mol % or less or silveriodobromide may be used. The average grain size of the above-mentionedsilver halide is preferable to be 0.05 to 0.5 μm, and most preferable tobe 0.10 to 0.40 μm.

Though the dispersion of grain sizes of silver halide grains used in thepresent invention is arbitrary, it is adjusted so that the value ofmono-dispersion degree defined below is in the range of 1 to 20%preferably and 5 to 15% more preferably.

Here, mono dispersion degree is defined as a value (%) wherein thestandard deviation of grain size is divided by the average grain sizeand the quotient therefrom is multiplied by 100. The grain size ofsilver halide grain is, for convenience' sake, represented by the edgelength for a cubic crystal grain and is calculated using the square rootof projected area for other grains (octahedron, tetrahedron and so on).

In working of the present invention, silver halide grains each having 2layers of multi layer lamination structure can be used. For example,those composed of silver iodobromide in the core portion and silverbromide in the shell portion thereof can be used. In such a case, iodinecan be contained in arbitrary layers in quantity of 5 mol % or less.

To silver halide grains used for a silver halide emulsion in the presentinvention, metal ion can be added employing at least one selected fromcadmium salts, zinc salts, lead salts, thallium salts, iridium salts(including their complex salts), rhodium salts (including their complexsalts) and iron salts (including their complex salts) in the course offorming grains and/or growing grains so that the above-mentioned metalelement may be contained in the inside and/or the surface of the grain.In addition, by placing them under reducing condition, reductivesensitization nucleus can be provided in the inside and/or on thesurface of grains.

In addition, silver halide can be sensitized by means of variouschemical sensitizers. As sensitizers, for example, active gelatin,sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea andallylisothiacynate), selenium sensitizers (N,N-dimethylselenourea andselenourea), reduction sensitizers (triethylenetetramine and stannouschloride) and various noble metal sensitizers can be used independently,or in combination of 2 or more of them. When a gold sensitizer is used,ammonium rhodanide can be used as an auxiliary agent.

Since silver halide grains used in the present invention can preferablybe used for grains wherein inside sensitivity for each grain is higherthan that on the surface thereof, so-called silver halide grainsproviding negative images, the performance thereof can be improved byprocessing with the above-mentioned chemical sensitizers.

In addition, silver halide emulsions used in the present invention canbe subjected to stabilization or fog-restraining through the use of amercapto group (for example, 1-phenyl-5-mercaptotetrazole and2-mercaptobenzthiazole), a benzotriazole group (5-bromobenzotriazole,5-methylbenzotriazole) and a benzoimidazole group(6-nitrobenzoimidazole).

To light-sensitive silver halide emulsion layers or adjacent layersthereof, compounds described in Items B to D of Item XXI of ResearchDisclosure Vol. 17463 can be added for the purpose of enhancingsensitivity, enhancing contrast or accelerating development.

In addition, compounds represented by the following Formula P arepreferable to be added.

    R.sub.11 --O--(CH.sub.2 CH.sub.2 O)nH

wherein R₁₁ represents a hydrogen atom or an aromatic ring having anunsubstituted or a substituted group; n represents an integer of 10 to200.

As practical examples of compounds represented by Formula P, P-1 to P-17described on pp. 94 to 96 of Japanese Patent Application No. 160939/1990are preferable. Of them, the molecular weight is preferable to be notless than 1500.

The above-mentioned compounds are on the market and are easilyavailable. They are preferable to be added by 0.01 to 0.4 mol inquantity per mol of silver halide, and more preferable to be added at0.02 to 2 mol. In addition, it is allowed to contain 2 or more compoundshaving different n values.

To a silver halide emulsion used in the present invention, a sensitizingdye, a plasticizer, an anti-static agent, a surfactant and a hardenercan also be added.

When compounds of Formulae I, II and III in the present invention areadded to hydrophilic colloidal layers, gelatin is preferably used for abinder to the hydrophilic colloidal layer. Hydrophilic colloids otherthan gelatin can also be used. The above-mentioned hydrophilic bindersare preferable to be coated at 10 g/m² or less on both side of support.

As a support capable of being used in working of the present invention,for example, a baryta paper, a polyethylene-laminated paper, apolypropyrene-synthesized paper, a glass plate, cellulose acetate,cellulose nitrate and polyester films such as polyethylene terephthalatecan be cited. The above-mentioned supports are selected appropriatelydepending upon the purpose of application of each silver halidephotographic light-sensitive material.

When a silver halide photographic light-sensitive material in thepresent invention is developed, the following developing agents areused.

A typical HO--(CH═CH)n--OH type developing agent is hydroquinone. Inaddition, catechol and pyrogallol are used.

In addition, as a HO--(CH═CH)n--NH₂ type developing agent, ortho andpara aminophenols or aminopyrazolones are typical.N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol,p-hydroxyphenylamino acetate and 2-aminonaphthol are cited.

As heterocycle type developing agents, 3-pyrazolidone types such as1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are cited.

In addition, developing agents described on pp. 291 to 334 of The Theoryof the Photographic Process, Fourth Edition and page 3,100 of Journal ofthe American Chemical Society Volume 73 (1951) can effectively beemployed in the present invention. The above-mentioned developing agentsmay be used independently, or 2 or more of them may be used incombination. However, it is preferable to use 2 or more of them incombination.

Even when sulfites such as soda sulfite and potassium sulfite are usedas a preserver for a developing solution used for developing alight-sensitive material in the present invention, the effect of thepresent is not damaged. In addition, hydroxylamine and hydrazidecompounds may also be used as preservers. In addition, functions of pHadjustment and buffering employing caustic alkali, alkali carbonate andamine as used in conventional black-and-white developing solution can beprovided.

As developing solutions used in the present invention, it is noticeablethat those having pH of less than 11 can be used. In addition, to thedeveloping solutions, it is arbitrary to add inorganic developmentinhibitor such as potassium bromide, organic development inhibitor suchas 5-methylbenzotriazole, 5-methylbenzoimidazole, 5-nitroindazole,adenine, guanine and 1-phenyl-5-mercaptotetrazole, scavengers for metalion such as ethylenediamine tetraactate, development accelerators suchas methanol, ethanol, benzylalcohol and polyalkyleneoxide, surfactantssuch as sodium alkylarylsulfonate, natural saponin, sugar, alkylestercompounds of the above-mentioned compound, hardeners such as glutaricaldehyde, formalin and glyoxal and adjuster of ion strength such assodium sulfate.

To developing solutions used in the present invention, as organicsolvents, alkanolamine group such as diethanolamine and triethanolamine,glycol group such as diethylene glycol and triethyleneglycol andalkylaminoalcohol group such as diethylamino-1,2-propanediol andbutylaminopropanol may be contained.

EXAMPLE

The following examples serves to illustrate the practice of theinvention.

However, it should be understood that the present invention is by nomeans restricted to such specific examples.

EXAMPLE 1 Preparation of Silver Halide Emulsion A

By means of the double jet method, silver iodobromide emulsion (havingsilver iodide of 2 mol % per mol of silver) was prepared. In thismixing, 8×10⁻⁷ mol of K₂ IrCl₆ were added per mol of silver.

The obtained emulsion was composed of cubic mono-dispersed grains (thecoefficient of variation was 9.5%) having an average grain size of 0.20μm. To the above-mentioned emulsion, 6.5 ml of 1% potassium iodideaqueous solution was added per mol of silver. Then, degenerated gelatin(an illustrated compound G-8 described in Japanese Patent ApplicationNo. 180787/1989). The solution was washed and desalted in the samemanner as Example 1 of Japanese Patent Application No. 180787/1989. pAgof the solution at 40° C. after subjected to desalting was 8.0. Inaddition, when the solution was subjected to dispersing again, themixture of the following compounds [A], [B]and [C] were added as anantibacteria agent. ##STR32##

Preparation of Silver Halide Photographic Light-sensitive Material

On one side of subbing layer (detailed in Example 1 of Japanese PatentApplication No. 1994/1984) having thickness of 0.1 μm provided on bothside of polyethylene terephthalate film having thickness of 100 μm, asilver halide emulsion layer shown in composition (1) was coated so thatthe amount of gelatin was 2.0 g/m² and the content of silver was 3.2g/m². In addition, an emulsion protective layer shown in composition (2)was coated thereon so that the amount of gelatin was 1.0 g/m². On theother subbing layer rear side, a backing layer having the followingcomposition (3) was coated so that the amount of gelatin was 2.4 g/m².In addition, a backing protective layer having the following composition(4) was coated thereon so that the content of gelatin was 1.0 g/m².Thus, the samples 1 to 30 were prepared.

    ______________________________________                                        Composition (1)                                                               (silver halide emulsion layer)                                                ______________________________________                                        Gelatin                   2.0    g/m.sup.2                                    Silver halide emulsion A (content of silver)                                                            3.2    g/m.sup.2                                    Sensitizing dye: SD-1     8.0    mg/m.sup.2                                   Sensitizing dye: SD-2     0.2    mg/m.sup.2                                   Stabilizer: 4-methyl-6-hydroxy-1,3,3a,7-                                                                30     mg/m.sup.2                                   tetrazaindene                                                                 Anti-foggant: Adenine     10     mg/m.sup.2                                   Surfactant: Saponin       0.1    g/m.sup.2                                    Surfactant: S-1           8.0    mg/m.sup.2                                   Hydrazine derivative in the invention                                                                   30     mg/m.sup.2                                   Contrast-promoting compound in the invention                                                            100    mg/m.sup.2                                   Latex polymer: LX         1.0    g/m.sup.2                                    Polyethylene glycol (the molecular weight is 4000)                                                      0.1    g/m.sup.2                                    Hardener: H-1             60     mg/m.sup.2                                   ______________________________________                                    

    ______________________________________                                        Composition (2)                                                               (emulsion protective layer)                                                   ______________________________________                                        Gelatin                    1.0   g/m.sup.2                                    Surfactant: S-2            10    mg/m.sup.2                                   Matting agent: Silica having an average grain size                                                       3     mg/m.sup.2                                   of 3.5 μm                                                                  Hardener: Formalin         30    mg/m.sup.2                                   Surfactant: S-3            10    mg/m.sup.2                                   ______________________________________                                    

    ______________________________________                                        Composition (3)                                                               (backing layer)                                                               ______________________________________                                        D-1                   30    mg/m.sup.2                                        D-2                   75    mg/m.sup.2                                        D-3                   30    mg/m.sup.2                                        Gelatin               2.4   g/m.sup.2                                         Surfactant: S-1       6.0   mg/m.sup.2                                        Surfactant: Saponin   0.1   g/m.sup.2                                         ______________________________________                                    

    ______________________________________                                        Composition (4)                                                               (backing protective layer)                                                    ______________________________________                                        Gelatin                    1     g/m.sup.2                                    Matting agent: polymethylmethacrylate having an                                                          15    mg/m.sup.2                                   average grain size of 3.0 to 5.0 μm                                        Surfactant: S-2            10    mg/m.sup.2                                   Hardener: glyoxal          25    mg/m.sup.2                                   Hardener: H-1              35    mg/m.sup.2                                   ______________________________________                                    

Compounds used in Compositions (1), (2) and (3) are shown as follows.##STR33##

The obtained samples were subjected to dots quality test employing thefollowing method.

The Method of Examination of Dot Quality

A contact dot screen having an dot area of 50% (150 lines/inch) wereprovided on a step wedge partially, to which a sample was contacted andsubjected to exposure for 5 seconds by means of Xenon electric source.The above-mentioned sample was subjected to development processing underthe following conditions employing an automatic developing machine forrapid processing use to which the following developing solution and thefollowing fixing solution were charged. Then, the dot quality of samplewas observed with a loupe with a 100=power magnifier. The supreme dotquality was ranked as "5", and the others were ranked as "4", "3", "2"and "1" as the quality was degraded in this order.

The ranks 1 and 2 each represent a level of no practical use.

In addition, fogging in dots were evaluated in the same manner. Thosewherein pepper fog did not occur in dots at all were ranked as thesupreme "5". Depending upon the degree of occurrence of pepper fogoccurred in dots, they were ranked as "4", "3", "2" and "1" wherein theevaluations were degraded as the numerals were decreased.

Incidentally, in ranks "1"and "2", pepper fog are so large that they arenot acceptable for practical use.

    ______________________________________                                                           Developing                                                                            Developing                                                            solution 1                                                                            solution 2                                         ______________________________________                                        Composition of developing solution                                            Sodium salt ethylenediamine                                                                        1       g     1     g                                    tetraacetate                                                                  Sodium sulfite       60      g     60    g                                    Trisodium phosphate (dodecahydrate)                                                                75      g     75    g                                    Hydroquinone         22.5    g     22.5  g                                    Sodium hydroxide     8       g     8     g                                    Sodium bromide       3       g     3     g                                    5-methylbenzotriazole                                                                              0.25    g     0.25  g                                    1-phenyl-5-mercaptotetrazole                                                                       0.08    g     0.08  g                                    Metol                0.25    g     0.25  g                                    Water to make        1       l.    1     l.                                   pH was adjusted with sodium hydroxide.                                                             pH = 10.8 pH = 10.5                                      Composition of fixing solution                                                (Composition A)                                                               Ammonium thiosulfate (aqueous solution of                                                                240    ml                                          72.5 w/v %)                                                                   Sodium sulfite             17     g                                           Sodium acetate (trihydrate)                                                                              6.5    g                                           Boric acid                 6      g                                           Sodium citrate (dihydrate) 2      g                                           (Composition B)                                                               Pure water (ion-exchanged water)                                                                         17     ml                                          Sulfuric acid (aqueous solution of 50% w/w)                                                              4.7    g                                           Aluminum sulfate           26.5   g                                           ______________________________________                                    

Aqueous solution wherein reduced amount converted to Al₂ O₃ is 8.1 w/w%.

When a fixing solution was used, the above-mentioned compositions A andB were dissolved in 500 ml of water in this order to make 1 l. pH ofthis fixing solution was adjusted to 4.8 with acetic acid.

    ______________________________________                                        (Conditions for development)                                                  (Step)       (Temperature)                                                                             (Time)                                               ______________________________________                                        Developing   40° C.                                                                             15 seconds                                           Fixing       35° C.                                                                             15 seconds                                           Washing      30° C.                                                                             10 seconds                                           Drying       50° C.                                                                             10 seconds                                           ______________________________________                                    

As comparative compounds for the contrast-promoting compounds in thepresent invention added in the silver halide emulsion layer in Formula1, the following Compounds (a) and (b) were added. ##STR34##

The results of quality test are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________        contrast-                                                                 Sample                                                                            promoting                                                                           Hydrazine                                                                           Developing                                                                          Dot Pepper                                              No. compound                                                                            compound                                                                            solution                                                                            quality                                                                           fog Note                                            __________________________________________________________________________     1  --    --    1     1   5   Comparative                                      2  --    III-5 1     2   5   Comparative                                      3  I-2   --    1     1   5   Comparative                                      4  I-2   III-5 1     4   4   Invention                                        5  I-3   III-8 1     4.5 4   Invention                                        6  I-3   III-8 2     4   4.5 Invention                                        7  I-3   III-12                                                                              1     5   4   Invention                                        8  I-3   III-12                                                                              2     4   4.5 Invention                                        9  I-3   III-22                                                                              1     4   3   Invention                                       10  I-3   III-22                                                                              2     3.5 4   Invention                                       11  I-3   III-29                                                                              1     3   4   Invention                                       12  I-4   III-8 1     4.5 4   Invention                                       13  I-11  III-12                                                                              1     5   4.5 Invention                                       14  I-11  III-12                                                                              2     4   5   Invention                                       15  (a)   III-12                                                                              1     2.5 3   Comparative                                     16  (a)   III-12                                                                              2     2   3.5 Comparative                                     17  (b)   III-12                                                                              1     4   2   Comparative                                     18  (b)   III-12                                                                              2     3   3   Comparative                                     19  I-12  III-12                                                                              1     4   4   Invention                                       20  I-17  III-16                                                                              1     4   4   Invention                                       21  I-20  III-5 1     4.5 4   Invention                                       22  I-20  III-5 2     4   5   Invention                                       23  I-20  III-12                                                                              1     5   4   Invention                                       24  I-20  III-12                                                                              2     4   5   Invention                                       25  I-20  III-18                                                                              1     3.5 5   Invention                                       26  I-22  III-8 1     4.5 4.5 Invention                                       27  I-34  III-12                                                                              1     5   4.5 Invention                                       28  I-34  III-12                                                                              2     4   5   Invention                                       29  I-34  III-16                                                                              1     4   5   Invention                                       30  I-44  III-5 1     4   4.5 Invention                                       __________________________________________________________________________

As is apparent from Table 1, the samples in the present invention aresuperior to the comparative samples in dot quality and pepper fog.

EXAMPLE 2

Samples were prepared in the same manner as Example 1 except that thecontrast-promoting compound represented by Formula [I] in (1) of Example1 was replaced with contrast-promoting compound represented by Formula[II] in the present invention and compounds shown in the following (a)and (b) were employed as comparative compounds. ##STR35##

The results of quality test are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________        contrast-                                                                 Sample                                                                            promoting                                                                           Hydrazine                                                                           Developing                                                                          Dot Pepper                                              No. compound                                                                            compound                                                                            solution                                                                            quality                                                                           fog Note                                            __________________________________________________________________________     1  (a)   III-12                                                                              1     4   2   Comparative                                      2  (a)   III-12                                                                              2     3.5 2.5 Comparative                                      3  (b)   III-12                                                                              1     4   2   Comparative                                      4  (b)   III-12                                                                              2     3   3   Comparative                                      5  II-3  III-12                                                                              1     5   4   Invention                                        6  II-3  III-12                                                                              2     4.5 4.5 Invention                                        7  II-3  III-33                                                                              1     5   4.5 Invention                                        8  II-3  III-33                                                                              2     4.5 5   Invention                                        9  II-4  III-12                                                                              1     5   4   Invention                                       10  II-4  III-12                                                                              2     4.5 4.5 Invention                                       11  II-4  III-22                                                                              1     4   3   Invention                                       12  II-4  III-22                                                                              2     3.5 4   Invention                                       13  II-4  III-39                                                                              1     5   4.5 Invention                                       14  II-8  III-5 1     4   4.5 Invention                                       15  II-8  III-12                                                                              1     4.5 4.5 Invention                                       16  II-9  III-12                                                                              1     5   4   Invention                                       17  II-9  III-12                                                                              2     4.5 4.5 Invention                                       18  II-10 III-12                                                                              1     4   4.5 Invention                                       19  II-14 III-12                                                                              1     4   4.5 Invention                                       20  II-14 III-39                                                                              1     4.5 4.5 Invention                                       21  II-18 III-5 1     4   5   Invention                                       22  II-18 III-33                                                                              1     4.5 4.5 Invention                                       23  II-18 III-33                                                                              2     4   5   Invention                                       24  II-21 III-12                                                                              1     4.5 4.5 Invention                                       25  II-21 III-35                                                                              1     4.5 4.5 Invention                                       26  II-21 III-35                                                                              2     4   5   Invention                                       27  II-24 III-8 1     4.5 4   Invention                                       28  II-34 III-30                                                                              1     5   4   Invention                                       29  II-34 III-30                                                                              2     4.5 5   Invention                                       __________________________________________________________________________

As is apparent from Table 2, it turns out the samples in the presentinvention are superior to the comparative samples in dot quality andpepper fog.

What is claimed is:
 1. A silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer, a hydrazine compound being contained in said silver emulsion layer or at least one other layer, wherein said material contains at least one compound represented by Formula I or Formula II, ##STR36## wherein R₁ and R₂ individually are alkyl, alkenyl, or alkynyl; R₁ and R₂ may form a ring; R₃ is hydrogen, alkyl, alkenyl, alkynyl, aryl or a heterocyclic group; L₁ is a divalent linking group; X is --[S--L₂ --Y--(L₃)n]-- or [--(L₃)n--Y--L₂ --S--]--, wherein L₂ is alkylene or alkenylene, Y is carbonyl, sulfonyl, sulfoxy, or phosphoryl, and L₃ is ##STR37## wherein Z₁, Z₂, and Z₃ individually are hydrogen, alkyl, alkenyl, alkynyl, aryl or a heterocyclic group; and n is an integer of 0 to 1; ##STR38## wherein R₄, R₅ and R₆ independently are alkyl, alkenyl or alkynyl, compounds of Formula II further comprising a thioether group and a group represented by --O--Y), wherein Y represents alkylene, alkenylene or arylene, and l is an integer of 2 or more.
 2. The silver halide photographic light-sensitive material of claim 1, wherein the compound represented by Formula II is the compound selected from the group consisting of Formula II-A and Formula II-B, ##STR39## wherein R₄ and R₅ independently are alkyl, alkenyl or alkynyl, Y' is alkylene, alkenylene or arylene, l is an integer of 2 or more, m and n are independently 0 or 1, L is a divalent aliphatic group, J₁ and J₂ individually are divalent linking groups, R' is an aliphatic group, an aromatic group, or a heterocyclic group, and R" is hydrogen, an aliphatic group, an aromatic group or a heterocyclic group.
 3. The silver halide light-sensitive material of claim 1, wherein said hydrazine compound is represented by Formula III, ##STR40## wherein A represents an aliphatic group, an aromatic group or a heterocyclic group, B represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group or a heterocyclic group, A₁ and A₂ both represent hydrogen atoms, or one of them represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group, wherein B, A₂ and a nitrogen atom bonded with B and A₂ may form a hydrazone structure represented by ##STR41##
 4. The silver halide photographic light-sensitive material of claim 1, wherein said hydrazine compound is represented by Formula IV, ##STR42## wherein R₇ represents an aryl group or a heterocyclic group, R₈ represents a ##STR43## wherein R₉ and R₁₀ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxyl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclicoxy group, R₁₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, A₁ and A₂ both represent hydrogen atoms, or one of them represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group.
 5. The silver halide photographic light-sensitive material of claim 1, wherein the content of a compound represented by Formula I or Formula II is within the range of 5×10⁻⁷ to 5×10⁻¹ mol/mol silver halide.
 6. The silver halide photographic light-sensitive material of claim 1, wherein a compound represented by Formula I or Formula II is contained in said silver halide emulsion layer or a hydrophilic colloidal layer adjacent to said silver halide emulsion layer.
 7. A silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer, a hydrazine compound being contained in said silver emulsion layer or at least one other layer, wherein said material contains at least one compound represented by Formula I, Formula II-A or Formula II-B, ##STR44## wherein R₁ and R₂ individually are alkyl, alkenyl, or alkynyl; R₁ and R₂ may form a ring; R₃ is hydrogen, alkyl, alkenyl, alkynyl, aryl, or a heterocyclic group; L₁ is a divalent combination group; X is --[S--L₂ --Y--(L₃)n]-- or [--(L₃)n--Y--L₂ --S--]--, wherein L₂ is alkylene or alkenylene, Y is carbonyl, sulfonyl, sulfoxy, or phosphoryl, and L₃ is ##STR45## wherein Z₁, Z₂, and Z₃ independently represent hydrogen, alkyl, alkenyl, alkynyl, aryl, or a heterocyclic group; n is an integer of 0 to 1, ##STR46## wherein R₄ and R₅ individually are alkyl, alkenyl, or alkynyl, Y' is alkylene, alkenylene, or arylene, l is an integer of 2 or more, m and n are independently 0 or 1, L is a divalent aliphatic group, J₁ and J₂ are individually divalent linking groups, R' is an aliphatic group, an aromatic group, or a heterocyclic group, and R" is hydrogen, an aliphatic group, an aromatic group, or a heterocyclic group. 